Process for giving shape-fitting property on a garment knitted with filament yarns

ABSTRACT

A method and composition for imparting wash durable, shapefitting properties to a filament yarn knitted garment, whereby a primer comprising a monomer or a prepolymer having the general formula R-Si-X3, wherein R is a radical having a double bond and X is a silicon atom-bonding organic radical, and a polyorganosiloxane is applied to said garment.

United States Patent 11113,632,423

[72] Inventor Masaki Kusuhara [56] References Cited Y v UNITED STATESPATENTS [21] P 69 2,597,614 5/1952 Brown et al 117/121 [22] d f' a2,702,276 2/1955 Green... 252/8.6 [45] t 3* Lu 2,807,601 9/1957 Dennett117/161 x [731 Assgnee T 1" 3,065,111 11/1962 Reeves et al.. 117/161[32] mom 2 m 3:; 3,345,195 10/1967 Simpson 117/1394 x y 3,392,040 7/1968Kass 117/161 X Jap [31] 42/1877 Primary ExaminerWilliam D. MartinAssistant Examiner-Theodore G. Davis Attorney-Oblon, Fisher and Spivak[54] PROCESS FOR GIVING SHAPE-FITTING PROPERTY ON A GARMENT KNITTED WITHFILAMENT YARNS ABSTRACT: A method and composition for imparting wash 10Claims, No Drawings durable, shape-fitting properties to a filament yarnknitted garment, whereby a primer comprising a monomer or a [52] US. Clp p y having the general formula wherein R [51 1 1m Cl Downs/66 is aradical having a double bond and X is a silicon atom-bond- Do6m 15/72,ing organic radical, and a polyorganosiloxane is applied to said [50Field of Search 117 1394, game 139.5 A, 161 ZA, 76 T, 121, 126 GS, 138.8N; 252/8.6; 260/825 PROCESS FOR GIVING SHAPE-FITTING PROPERTY ON AGARMENT KNITTED WITH FILAMENT YARNS BACKGROUND OF THE INVENTION 1 Fieldof Invention This invention relates to a process for impartingshapefitting properties to a filament yarn knitted garment, such ashosiery, body stockings, tights, panties, gloves, or brassieres.

2. Description of Prior Art Garments prepared from knitted filamentyarns, such as hosiery, body stockings, tights, panties, gloves orbrassieres, will often wrinkle during wear thereby causing the garmentto only partially contact the body of the wearer. This places a greaterload on the wearers body at the wrinkling points, which is frequentlysufficient to suppress the circulation of the blood and leave unsightlymarks when the garment is worn directly on the body without someprotective undergarment. To resolve these difficulties, it has beenproposed to use hightwisted yarns, or crimp yarns, to impart elasticityto the gar- 2 ment. The fitting properties based on the elasticity ofthe hightwisted yarns, or crimp yarns, however, is insufficient toprevent the high-contractile forces and partial strains which suppressblood circulation.

SUMMARY OF THE INVENTION It is therefore an object of this invention toprovide a process for rendering shape-fitting properties to a garmentknitted with filament yarns which can be worn directly on the wearer'sbody without a protective undergarment.

It is another object of this invention to provide a process for usingspecific chemicals to render wash durable shape-fitting properties to agarment knitted with filament yarns.

It is a further object of this invention to provide a process for usingspecific chemicals to provide wash durable, shapefitting properties to agarment knitted with twisted filament yarns.

These and other objects have now herein been obtained by treating theknitted garment with a monomer or prepolymer having the general formula(RSiX wherein R is a radical having a double bond, X is asilicon-atom-bonding organic radical, and q is an integer from I to 5,and a polyorganosiloxane.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Garments knitted withfilament yarns are commonly used in preparing ladies hosiery. For thispurpose, filament yarns of 10 to 30 total deniers, and especially 15total deniers, e.g., 5 denier X 3 fil., 7.5 denier X 2 fil., or 15denier X lfil. are used. The filament yarns may be twisted, such as inalternate S-twist yarns, and Z-twist yarns, to make the knitted courses.Also, ply yarns having S-twist yarns and Z-twist yarns are frequentlyused. A crimp yarn which is produced by twisting heat-set detwisting, orby knipping, may be used. A crimping yarn made of conjugate yarn mayalso be used for knitting the garment to be treated by the process ofthis invention. Even nontwist yarns may be used to impart a slightstress to the knitted garment. The garment may be knitted with acircular knitting machine, a flat knitting machine, or a warp knittingmachine.

The knitted fabric used for this invention is shaped into a garment,such as ladies seamless hosiery, tights produced with a circularknitting machine, body stockings produced with a circular knittingmachine, panties, gloves, etc.

Although it has been proposed to provide water repellency to the fibersby treating them with emulsions of silicon resins, such as methylhydrogen polysiloxane dispersed in water, or by dipping the yarns intosolutions of emulsions of methylpolysiloxane and methyl-hydrogenpolysiloxane mixtures and then heat-drying, these processes do notimpart wash durable fitting properties to the knitted filament yarns.

In accordance with the present invention, wash durable fittingproperties are imparted to the garment by using a primer comprising:

A. A monomer or prepolymer having no more than five units, having thegeneral formula RSiX;,, wherein R is selected from the group ofCH =CH,CH;,-CH=CH,

CH=CH X is selected from a silicon-atom-bonding organic radical such asOCI-l-,,, OC H OC H OC I-I OC,=,H,,, OC I-I OC H, OC,,H,,, 2-aminoethyl,3-aminopropyl, 4-aminobutyl and 5- aminophenyl, and

B. a polyorganosiloxane having the general formula i \tWL It wherein Yis OH or Cl, and more than two Ys are in the formula but the ratio ofY/R is less than 0.1;

n is an integer of more than 5, preferably from 100 to 3000; I

R is an alkyl group (methyl, ethyl, tertiary-butyl, etcr), an alkenylgroup (vinyl, allyl, hexenyl, etc.), a cycloaliphatic hydrocarbon group(cyclohexyl, cyclopentyl, etc.), an alkylaryl group (benzyl,phenylethyl, etc.) or an aryl group (phenyl, toluyl, xylyl, naphthyl,etc.).

The primer (A) and polyorganosiloxane (B) may be applied to the garmentknitted with filament yarns in a one-step process by using the mixtureof primer (A) and polyorganosiloxane (B) or by sequentially passing thegarment through each of (A) and (B), In a two-step process, the garmentis dipped into the primer (A) and dried and then dipped into a solutionof the polyorganosiloxane (B).

The polyorganosiloxane solution may also contain a modifier such as amonomer or a prepolymer having no more than five units, of the followinggeneral formula:

When Y in the polyorganosiloxane is OH, the formulated modifier is:

R 'C=NOH wherein R" is the same as defined above.

When a twostep process is used, the solution of the polyorganosiloxanemay contain an accelerant together with the modifier.

When 2 of the modifier is an acetyl group, the accelerant is selectedfrom the group of dibutyl-tin-diacetate, dibutylzinc-diacetate,dibutyl-lead diacetate.

When any of the other modifiers are used, the accelerant may be a saltof an organic carboxylic acid such as lead, tin, antimony, iron, or abarium salt of linoleic acid, stearic acid, acetic acid, or butylicacid.

When the modifier is R"C=NOH, the accelerant may be an organic aminesuch as di-n-hexamine.

A nonaqueous solvent such as benzene, toluene, xylene, petroleum ether,perchloroethylene, or chlorobenzene may be used for mixing thepolyorganosiloxane, the modifier, and the 75 accelerant.

llllOl'I The quantity of the polyorganosiloxane in the mixture is 70 to90 weight percent, and the quantity of the modifier is 20 to 1 weightpercent. When more than 20 weight percent of the modifier is used, thereaction is not uniform, and when less than l percent of the modifier isused, the desired effect is reduced. The quantity of the accelerant is 5to O.l weight percent. When more than 5 weight percent is used, thereaction is too fast and when less than 0.l weight percent is used, thedesired effect is reduced.

The solution, diluted with the nonaqueous solvent, is applied to thegarment by dipping or spraying. it is preferably to treat the garment sothat each crossing part of knitted warp of filament yarns is immersed.The concentration of the polyorganosiloxane solution is preferablybetween about 0.1 to 3 weight percent. in amounts of less than 0.1weight percent, the desired effect is reduced. When more than 3 weightpercent of polyorganosiloxane is used, the softness of the garment maybe lost.

When the two-step procedure is used, the garment is first pretreatedwith a primer (A). For this purpose, a solution of 1-20 weight percentof the primer is prepared with an organic solvent such as methanol,perchloroethylene, or petroleum' ether. if the concentration of theprimer is higher than percent, the garment tends to lose its softness. Apolymerization catalyst such as triethoxy-titane, may be used when thesolution is intended to be dipped or sprayed onto the garment.

The treated garment is dried at a relatively low temperature, such asbetween room temperature and 50 Centigrade. During the treatment, theprimer is polymerized and is adhered to the filament yarns of thegarment. in selecting the particular primer, therefore, it is necessaryto consider the affinity of the particular primer for the particularfilament yarn.

After the pretreatment, the garment is treated with a nonaqueoussolution of a polyorganosiloxane containing the modifier and theaccelerant. The polyorganosiloxane and the modifier is reacted on thefilament to form a slippery covering over the polymerized primer coveredfilament yarn.

When a one-step procedure is used, the garment is treated with thenonaqueous solution of the primer and the organosiloxane diluted withthe nonaqueous solvent containing, if necessary, the modifier or theaccelerant by dipping or spraying the garment with the solution so as toimmerse each of the crossover parts of the filament yam.

The garment treated with the solution is dried at a relatively lowtemperature such as between about room temperature and Centigrade. Inthe one-step process, the primer is partially polymerized and adhered tothe filament yarn, and the polyorganosiloxane is reacted so as to adhereto the product so as to make the filament yarn slippery. Thisslipperiness is wash durable.

The shape-fitting properties of the garment treated by the process ofthe present invention is imparted by the slippery movement of thefilament yarns which reduces the tensile strength built up by partialcontacts with the body. This shapefitting characteristic can bedemonstrated by the following test procedure.

A hosiery knitted with a circular knitting machine using twisted nylonfilament of 5 d. X 3 fil. (knitted by alternate S- twist and Z-twistyarns) are treated as follows:

The shape-fitting properties of the hosiery treated by both the one-stepand two-step processes were measured by observing the degree of wrinklesappearing at the ankles and knees of the garments when worn by 10different ladies. The degree of wrinkles are classified in the following10 types.

Shape-Fitting Property Degree OfWrinkling Produced Upon Bending The Lcg4 wrinkling remains for 5 in 7 persons.

Degree of wrinkling is too high 2 Sluck and wrinkle remain for all 10persons. l Degree of slack and wrinkle is too high.

EXAMPLE Hosiery knitted with a circular knitted machine by using eachtwisted nylon filament yarn of 5d. X 3 fit. was treated by the two-stepprocess or the one-step process using the following solutions, and driedat 40 Centigrade. The shape-fitting properties of each hosiery treatedby said process is shown in the table.

2. 0.1% perehloroethylene solution oi:

(B) polydimethylsilanol (C) triethoxymethylsilane (15%).

. 1. Treating with (3)-1. J 9

2. 0.1% perchloroethylene solution 01:

(B) polydimethyloxanechlorido (85%). (C) aoetoxim (10%). (D)di-n-hexyiarniuo (5%).

(5).... 1. 1% petroleum benzene solution of: (A) 8 titriisopropyloxyvinylsilane. 2. 0.1% petroleum benzene solution of:

(B) polyphenylmothylsilane (85%). (C) methyitriaeetoxysilane (15%).

(7).... 1. 1% petroleum benzene solution 01: (A) 8 Btriisopropyloxyvinylsilane. 2. 0.1% petroleum benzene solution oi:

(B) polyphenylmethylsilanol (85%). (C) triisopropyloxyethylsilane (12%).(D) barium butylate (3%).

(8)-... 1. A% petroleum benzene solution of: (A) 8 8triisopropyloxyvinylsilane. 2. 0.1% petroleum benzene solution of:

(B) polyphenylruethylsiloxaneehloride (85%). (C) diethylketoxirne (15%).

(0).... 1. 1% petroleum ether solution of: (A) tri-t- 8 8butyloxyallylsilano. 2. 0,1% petroleum other solution of:

(B) polydiphenylsllanol (85%). (C) triacetoxyphenylsilane (15%).

(11)... 1. 1% xylene solution oi: (A) tri-aminopropylvinylsilane. 2.0.1% xylene solution of:

(B) polyvinylmethylsilanol (85%). (C) triacetoxyvinylsilane (15%),

(12)... 1. 1% xylene solution of: (A) tri-amlno- .1 it

propylvinylsilane. 2. 0.1% xylene solution of:

(B) polyvinylmethylsilanol (85%). (C) tripropyloxyoinyisilane (15%).

(1:1)...1. 1% xylmin solution of: (A) trieuninopronylvlllylsilmio.2.111%xylnnosolutlonnf:

(ll) mlydiothyl-silsu'iol (85%). trim-.ntoxyothylsilnno (12%). (1))iibntyl-zinc-riiuootnto (3%).

ill

Shnpe-iltting property After washing with of soap solution for 5 minuteso v n 1. 1% toluene solution of: (A) triethoxystyrylsilnnv.

.5. 0.1% tolumm solution of:

(i1) pnlyeyolohoxylsllanol (35%).

((7) triaoutoxybutylsilnno (15%).

(16) 11.1% petroleum lionzono solution oi: (A) triethoxyvlnylsilano(111%). polydlmethylslianol (85%).

(C) triethoxymethylsilano (5%).

(17) (1.1% petroleum benzene solution oi: J

(A) trilsopropyloxyvinylsllano (15%). (1)) polyphenylmethylsiianol(85%).

0.1% petroleum benzene solution of: 51 .1

(A) triethoxyallylsllane (15%). (ii) polydimothylsilanol (85%).

(111) 0.1% petroleum benzene solution oi:

(A) triisopropyloxyallylsilane (ii) poiyphenylmethylsilonoi (75%). (C)triisopropyloxyethylsiluin: (5%).

(30) V 0.1% porchloroethylono solution of: J

(A) triethoxystyrylsllano (ii) polydirnetliylsilanol (115%).

(1.1% xylene solution 01: J 2| (A) trl-aminopropylvlllylsllnito (15%).(13) poiydimethylsllnnol (215%).

0.1% xylene solution of:

(A) trl-anlinopropylallylsilano (15%). (ll) polyphony]mothyi iinnol(115%).

(23) 0.1'7,1 xylene solution 01:

(A) tri4-aminolmtylstyryisliano (15%). (ii) polydiphoilyisilanoi (85%).

Stress-strain Diagram in order to demonstrate the changes of physicalproperties of the hosiery, stress-strain diagrams were measured by thetension tester for the samples of( 1), (2) control (3), (5), (6) and(10) as listed above.

TABLE ll.-FlRST STRETCHlNU-SilRlNKlNtl S-S DIAGRAM Elon- Treatmentstated in Table I, g,

gation, Percent (2) Stretching. 10 30 30 10 10 10 10 30 160 100 50 80 9080 30 300 220 170 205 210 220 40 A0 380 290 330 320 350 50 600 530 410460 440 510 Shrinking -10 185 1210 160 190 190 200 31 55 till 50 70 7O70 it) ill 10 10 10 10 ill 0 0 t) 0 0 0 TABLE 111. -FIRSI STRETCHlNti-SHRINKING 8-8 1) 1A U RAM Elon- Treatment stated in Table I,g.

gation, percent (2) Stretching. 10 0 0 0 O 5 5 20 50 40 20 40 40 40 30200 180 130 160 160 170 'lAlllrll 111. FIRST S'lltIITClllNG-SllRlNKlNliS-S l)lA(l RAM Shrinking 41] 160 180 180 Ill) 30 50 50 50 60 60 (K) 21)10 10 10 10 10 10 10 0 0 0 0 0 0 These tests show that the tensionstrength of these samples (3), (5), (6), (10) treated by this inventionunder stretching were extremely low in comparison with those of samples(I) or control sample (2). it was also found that the size of thehysteresis loop of the S-S diagram of the samples (3), (5), (6) and 10)treated by this invention, were extremely small in comparison with thoseof samples 1 and control sample (2).

Moreover, the differences in the hysteresis loop in the Firststretching-shrinking and the Second stretching-shrinking were minor.

The results of the stress-strain diagram measurements show that eachhosiery treated by (3), (5), (6) and (10) of this invention has goodshape characteristics, good softness and elasticity, which lattercharacteristics determine the shapefitting properties.

it should be understood that numerous modifications and variations ofthe present invention are possible in light of the above teachings. itis therefore to be understood that within the scope of the appendedclaims, the invention may be practiced otherwise than as specificallydescribed herein.

What is claimed and intended to be covered by Letters Patent is:

l. A process for imparting good shape-fitting characteristics to afilament yarn knitted garment, which comprises applying to said garmenta combination of:

A. a primer of the general formula:

(RSi-X wherein R is selected from the group consisting of CH =CH.

X is a radical selected from the group consisting of OCH;,, H: a h -1,1. E W ti Hh H. K I'Iv aminoethyl, 3-aminophcnyl, 4-aminobutyl, andS-aminophenyl, and q is an integer of from l-S;

B. a polyorganosiloxane having the general formula:

wherein Y is selected from the group consisting of OH and Cl and R isselected from the group consisting of R and Y, and wherein the ratio ofY/R' is less than 0.1,

n is an integer of more than 5;

R is selected from the group consisting of an alkyl group,

an alkenyl group, a cycioaliphatic hydrocarbon group,

an alkylaryl group and an aryl group.

2. The process of claim 8, wherein said garment is first immersed in A,dried and immersed in B.

3. The process of claim 1, wherein said garment is immersed into anadmixture ofA and B.

4. The process of claim 1, wherein n in the formula of .B is an integerof from between 100 and 3000.

5. The process of claim 8, wherein said combination contains a modifiersuch that when Y in the polyorganosiloxane is OH, said modifier ischaracterized by the formula:

3)q wherein R" is selected from thegroup consisting of an alkyl group,an alkenyl group, a cycloaliphatic hydrocarbon group,

an alkyl-aryl group. an aryl group, Z is selected from the groupconsisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, l-butoxy,and acetyl, and wherein q is an integer of from l to when Y in thepolyorganosiloxane is C], said modifier is characterized by the formula:

R 'C=N--Ol-l wherein R" is the same as defined above. I

6. The process of claim 5, wherein said garment is first immersed in(A), dried and then immersed in anadmixture of (B), said modifier, andan accelerant such that when Z of said modifier is an acetyl group, theaccelerant is selected from the group consisting ofdibutyl-tin-diacetate, dibutyl-zincdiacetate, anddibutyl-lead-diacetate,

when Z of said modifier is selected from the group consisting ofmethoxy, ethoxy, propoxy, isopropoxy, butoxy, and l-butoxy, theaccelerant is selected from the group consisting of an organiccarboxylic acid salt of a metal selected from the group consisting oflead, tin, antimony, iron and barium, and when said modifier isR'-C=NOH, said accelerant is an organic amine.

7. The process of claim 6, wherein said metal salt is a metal salt oflinoleic acid, stearic acid, acetic acid, or butylic acid.

8. The process of claim 1, wherein said primer is in the form of anonaqueous solution.

9. A process for producing a garment having wash-durable, shape-fittingproperties which comprises applying to said garment a combination of:

A. a primer of the general formula:

3) wherein R is selected from the group consisting of and CH=CH.

X is a radical selected from the group consisting of OCH wherein Y isselected from the group consisting of OH, Cl and R' is selected from thegroup consisting of R and Y and wherein the ratio of HR is less than 0.l;

n is an integer of more than 5;

R is selected from the group consisting of an alkyl group,

an alkenyl group, a cycloaliphatic hydrocarbon group, al-.

X is a radical selected from the group consisting of OCH,, Z Si OCEHW 4ll b lh OCGHHI (X-TTHLM n Ih aminoethyl, 3'aminophenyl, 4-aminobutyl,and S-aminophenyl, and q is an integer of from 1-5;

B. 70 to weight percent of a polyorganosiloxane in a nonaqueoussolution, said polyorganosiloxane having the general formula:

wherein Y is selected from the group consisting of OH or Cl and R isselected from the group consisting of R or Y, and wherein the ratio ofY/R' is less than 0.1;

n is an integer of more than 5; R is selected from the group consistingof an alkyl group, an alkenyl group, a cycloaliphatic hydrocarbon group,an alkylaryl group and an aryl group.

2. The process of claim 8, wherein said garment is first immersed in A,dried and immersed in B.
 3. The process of claim 1, wherein said garmentis immersed into an admixture of A and B.
 4. The process of claim 1,wherein n in the formula of B is an integer of from between 100 and3000.
 5. The process of claim 8, wherein said combination contains amodifier such that when Y in the polyorganosiloxane is OH, said modifieris characterized by the formula: (R''-Si-Z3)q wherein R'''' is selectedfrom the group consisting of an alkyl group, an alkenyl group, acycloaliphatic hydrocarbon group, an alkyl-aryl group, an aryl group, Zis selected from the group consisting of methoxy, ethoxy, propoxy,isopropoxy, butoxy, 1-butoxy, and acetyl, and wherein q is an integer offrom 1 to 5; when Y in the polyorganosiloxane is Cl, said modifier ischaracterized by the formula: R''''-C N-OH wherein R'''' is the same asdefined above.
 6. The process of claim 5, wherein said garment is firstimmersed in (A), dried and then immersed in an admixture of (B), saidmodifier, and an accelerant such that when Z of said modifier is anacetyl group, the accelerant is selected from the group consisting ofdibutyl-tin-diacetate, dibutyl-zinc-diacetate, anddibutyl-lead-diacetate, when Z of said modifier is selected from thegroup consisting of methoxy, ethoxy, propoxy, isopropoxy, butoxy, and1-butoxy, the accelerant is selected from the group consisting of anorganic carboxylic acid salt of a metal selected from the groupconsisting of lead, tin, antimony, iron and barium, and when saidmodifier is R''-C NOH, said accelerant is an organic amine.
 7. Theprocess of claim 6, wherein said metal salt is a metal salt of linoleicacid, stearic acid, acetic acid, or butylic acid.
 8. The process ofclaim 1, wherein said primer is in the form of a nonaqueous solution. 9.A process for producing a garment having wash-durable, shape-fittingproperties which comprises applying to said garment a combination of: A.a primer of the general formula: (R-Si-X3)q wherein R is selected fromthe group consisting of
 10. A process for imparting good shape-fittingcharacteristics to a filament yarn knitted garment, which comprises:applying to said garment a combination of: A. 20 to 1 weight percent ofa primer in a nonaqueous solvent, said primer having the generalformula: (R-Si-X3)q wherein R is selecteD from the group consisting ofCH2 CH-,